Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B41/00—Special methods of performing the coupling reaction
  • C09B41/006—Special methods of performing the coupling reaction characterised by process features
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/008—Preparations of disperse dyes or solvent dyes

Definitions

• the present invention describes an environment-friendly and economic process for preparing azo colorants.
• azo colorants are those azo dyes and azo pigments that are prepared by azo coupling reaction from a diazonium salt and a CH-acidic compound, referred to inter alia as coupling component hereinbelow (Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, “Azo Dyes” and “Azo Pigments”; and DIN 55943).
• a diazonium salt and a CH-acidic compound referred to inter alia as coupling component hereinbelow
• coupling component hereinbelow
• a feature common to these processes is the need for precise monitoring and control of the process parameters: for example, temperature, time, mixing, and colorant concentration—the suspension concentration in the case of azo pigments, for example—are critical to the yield, quality consistency, and coloristic and fastness properties of the resulting azo colorants.
• temperature, time, mixing, and colorant concentration the suspension concentration in the case of azo pigments, for example—are critical to the yield, quality consistency, and coloristic and fastness properties of the resulting azo colorants.
• the scaleup of new products from laboratory to industrial scales is complex and may cause difficulties, since, for example, tank and stirrer geometries or heat transitions may greatly affect the azo pigment particle size and its distribution, and the coloristic properties.
• microreactors are constructed, for example, from stacks of grooved plates with microchannels and are described in DE 39 26 466 C2 and U.S. Pat. No. 5,534,328.
• U.S. Pat. No. 5,811,062 notes that microreactors are used preferentially for reactions which do not require or produce solids, since the microchannels easily become clogged.
• the present invention provides a process for preparing azo colorants which comprises spraying the reactants, i.e. the coupling component and the diazonium salt, in their solution or suspension form through nozzles to a point of conjoint collision in a reactor chamber enclosed by a housing in a microjet reactor, appropriately via one or more pumps, preferably high-pressure pumps, a gas or an evaporating liquid being passed into the reactor chamber through an opening in the housing for the purpose of maintaining a gas atmosphere in the reactor chamber, especially at the point of collision of the jets, and where appropriate of effecting cooling as well, and the resulting product solution or suspension and the gas or the evaporated liquid being removed from the reactor through a further opening in the housing by means of overpressure on the gas entry side or underpressure on the product and gas exit side.
• the reactants i.e. the coupling component and the diazonium salt
• Preparation of azo colorants in accordance with the invention requires intensive, rapid, uniform, and reproducible mixing of the reactants. This is brought about by spraying the reactants used into the reactor chamber under a pressure of at least 10 bar, preferably at least 50 bar, in particular from 50 to 5000 bar.
• the collision point is shifted into the material-remote gas space.
• material-remote here is meant that, in the vicinity of the collision point of the jets, a gas atmosphere is maintained by means of the introduced gas or evaporating liquid. This means that the collision point at which the jets impinge on one another is not sited on a vessel wall or on a pipe wall. This prevents the material wear that would occur at the point where cavitation takes place on material walls. Cavitation occurs particularly when using high pressures, especially at pressures above 3000 bar. Moreover, the colliding jets are not braked by the gas atmosphere prior to their collision, as would be the case, for example, if they had to pass through a liquid.
• the material of the nozzles should be as hard and thus low-wearing as possible; examples of suitable materials include ceramics, such as oxides, carbides, nitrides or mixed compounds thereof, with preference being given to the use of aluminum oxide, particularly in the form of sapphire or ruby, although diamond is also particularly suitable. Suitable hard substances also include metals, especially hardened metals.
• the bores of the nozzles have diameters of less than 2 mm, preferably less than 0.5 mm and in particular less than 0.4 mm.
• the microjet reactor may be configured in principle as a two-jet, three-jet or multijet reactor, preference being given to the two-jet configuration.
• the jets preferably strike one another frontally (180° angle between the jets); in the case of a three-jet arrangement, an angle of 120° between the jets is appropriate.
• the jets advantageously may be mounted in a device which can be adjusted to the point of conjoint collision. As a result of these different embodiments it is possible, for example, to realize different volume ratios of the diazonium salt and coupling component solutions or suspensions which are required for the reaction.
• the coupling component solution or suspension and the diazonium salt solution or suspension are sprayed against one another frontally through two opposed nozzles by means of two high-pressure pumps.
• a further particularly preferred embodiment of the process of the invention is a three-jet reactor in which, for example, by means of a high-pressure pump the diazonium salt solution or suspension is sprayed to the point of conjoint collision through one nozzle and by means of a second high-pressure pump the coupling component solution or suspension is sprayed to the same point through two nozzles.
• the diazonium salt or suspension is sprayed to a point of conjoint collision through 1, 2 or more nozzles, preferably through one nozzle, and independently thereof the coupling component solution or suspension is sprayed to the same point through 1, 2 or more nozzles, preferably through 1, 2 or 3 nozzles.
• the nozzle of the diazonium salt solution or suspension and that of the coupling component solution or suspension may have different diameters.
• the nozzle through which the diazonium salt is sprayed appropriately has a diameter which is from 0.2 to 5 times, preferably from 0.3 to 3 times, that of the nozzle through which the coupling component is sprayed.
• the temperatures of the reactants are normally from ⁇ 10 to +90° C., preferably from ⁇ 5 to +80° C., particularly from 0 to 70° C. It is also possible to operate under pressure at above the boiling point of the liquid medium.
• the introduced gas or the evaporating liquid that is used to maintain the gas atmosphere in the inside of the housing may be used for cooling.
• an evaporating cooling liquid or a cooling gas may be introduced into the reactor chamber by way of an additional bore in the housing.
• the aggregate state of the cooling medium may be conditioned by temperature and/or pressure.
• the medium in question may comprise, for example, air, nitrogen, carbon dioxide or other, inert gases or liquids having an appropriate boiling point under increased pressure. It is possible here for the transition of the cooling medium from the liquid to the gaseous state to take place in the reactor itself by virtue of the fact that heat released in the course of the precipitation brings about the change in aggregate state. It is also possible for the evaporative cooling of an expanding gas to be utilized for cooling.
• the housing enclosing the reactor chamber may also be constructed in such a way that it is thermostatable and may be used for cooling; or else the product may be cooled after it has exited the housing.
• the pressure in the reactor chamber may, for example, be set and maintained by means of a pressure maintenance valve, so that the gas used is present in the liquid or supercritical or subcritical state.
• a pressure maintenance valve so that the gas used is present in the liquid or supercritical or subcritical state.
• the energy required for heating may be supplied prior to the emergence from the nozzles of the reactants—for example, in the supply lines—or by way of the thermostatable housing or the introduced gas.
• the chosen temperature may. also be situated a considerable way above the boiling point of the liquid medium.
• Suitable liquid media therefore include those which, at the temperature of reaction in the interior of the housing under atmospheric pressure, are present as gases.
• the reactants may also differ in temperature.
• the process of the invention is suitable for all azo colorants which can be prepared by azo coupling reaction: for example, for azo pigments from the series of the monoazo pigments, disazo pigments, ⁇ -naphthol and Naphtol AS pigments, laked azo pigments, benzimidazolone pigments, disazo condensation pigments and metal complex azo pigments; and for azo dyes from the series of the cationic, anionic, and nonionic azo dyes, especially monoazo, disazo and polyazo dyes, formazan dyes and other metal complex azo dyes, and anthraquinone azo dyes.
• the process of the invention also relates to the preparation of precursors of the actual azo colorants by azo coupling reaction.
• precursors for laked azo colorants i.e., lakeable azo colorants
• for diazo condensation pigments i.e., monoazo colorants which can be linked via a bifunctional group or, for example, disazo colorants which can be extended via an acid chloride intermediate, for formazan dyes, or other heavy metal azo dyes, examples being copper, chromium, nickel or cobalt azo dyes, i.e., azo colorants which can be complexed with heavy metals (see also “The Chemistry of Synthetic Dyes”, K. Venkataraman, Academic Press).
• the azo dyes comprise in particular the alkali metal salts or ammonium salts of the reactive dyes and also of the acid wool dyes or substantive cotton dyes of the azo series.
• Azo dyes under consideration include preferably metal-free and metalizable monoazo, disazo, and polyazo dyes, and azo dyes containing one or more sulfonic acid groups.
• the compounds involved in the case of the azo pigments include in particular C.I. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 65, 73, 74, 75, 81, 83, 97, 98, 106, 111, 113, 114, 120, 126, 127, 150, 151, 154, 155, 174, 175, 176, 180, 181, 183, 191, 194, 198, 213; Pigment Orange 5, 13, 34, 36, 38, 60, 62, 72, 74; Pigment Red 2, 3, 4, 8, 9, 10, 12, 14, 22, 38, 48:1-4, 49:1, 52:1-2, 53:1-3, 57:1, 60, 60:1, 68, 112, 137, 144, 146, 147, 170, 171, 175, 176, 184, 185, 187, 188, 208, 210, 214, 242, 247
• the compounds involved comprise, in particular, C.I. Reactive Yellow 15, 17, 23, 25, 27, 37, 39, 42, 57, 82, 87, 95, 111, 125, 142, 143, 148, 160, 161, 165, 168, 176, 181, 205, 206, 207, 208; Reactive Orange 7, 11, 12, 13, 15, 16, 30, 35, 64, 67, 69, 70, 72, 74, 82, 87, 91, 95, 96, 106, 107, 116, 122, 131, 132, 133; Reactive Red 2, 21, 23, 24, 35, 40, 49, 55, 56, 63, 65, 66, 78, 84, 106, 112, 116, 120, 123, 124, 136, 141, 147, 152, 158, 159, 174, 180, 181, 183, 184, 190, 197, 200, 201, 218, 225, 228, 235, 238, 239,
• the reactants in the form of aqueous solutions or suspensions, and preferably in equivalent amounts, to the microjet reactor.
• the azo coupling reaction takes place preferably in aqueous solution or suspension, although it is also possible to use organic solvents, alone or as a mixture with water; by way of example, alcohols having from 1 to 10 carbon atoms, examples being methanol, ethanol, n-propanol, isopropanol, butanols, such as n-butanol, sec-butanol, and tert-butanol, pentanols, such as n-pentanol and 2-methyl-2-butanol, hexanols, such as 2-methyl-2-pentanol and 3-methyl-3-pentanol, 2-methyl-2-hexanol, 3-ethyl-3-pentanol, octanols, such as 2,4,4-trimethyl-2-pentanol, and cyclohexanol; or glycols, such as ethylene glycol, diethylene glycol, propylene glycol, dipropy
• Reactants used for the azo coupling reaction are diazonium salts of aromatic or hetaromatic amines, such as, for example, aniline, 2-nitroaniline, methyl anthranilate, 2,5-dichloroaniline, 2-methyl-4-chloroaniline, 2-chloroaniline, 2-trifluoromethyl-4-chloroaniline, 2,4,5-trichloroaniline; 3-amino-4-methylbenzamide, 2-methyl-5-chloroaniline, 4-amino-3-chloro-N′-methylbenzamide, o-toluidine, o-dianisidine, 2,2′,5,5′-tetrachlorobenzidine, 2-amino-5-methylbenzenesulfonic acid, and 2-amino-4-chloro-5-methylbenzenesulfonic acid.
• diazonium salts of aromatic or hetaromatic amines such as, for example, aniline, 2-nitroaniline, methyl anthranilate, 2,5-
• azo pigments Of particular interest for azo pigments are the following amine components:
• n is a number from 0 to 3
• R 1 can be a C 1 -C 4 -alkyl group, such as methyl or ethyl; a C 1 -C 4 -alkoxy group, such as methoxy or ethoxy; a trifluoromethyl group; a nitro group; a halogen atom such as fluorine, chlorine or bromine; a NHCOCH 3 group; an SO 3 H group; a group SO 2 NR 10 R 11 where R 10 and R 11 are identical or different and are hydrogen or C 1 -C 4 alkyl; a group COOR 10 where R 10 is as defined above; or a group COONR 12 R 13 where R 12 and R 13 independently are hydrogen, C 1 -C 4 alkyl or phenyl, the phenyl ring being substituted by one, two or three identical or different substituents from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, trifluoromethyl, nitro, halogen, COOR 10 , R
• n>1R 1 may be identical or different;
• X is hydrogen, a COOH group or a group of the formula (III), (VI) or (VII);
• n and R 1 are as defined above;
• R 20 is hydrogen, methyl or ethyl
• n and R 1 are as defined above,
• Q 1 , Q 2 and Q 3 may be identical or different and are N, NR 2 , CO, N—CO, NR 2 —CO, CO—N, CO—NR 2 , CH, N—CH, NR 2 —CH, CH—N, CH—NR 2 , CH 2 , N—CH 2 , NR 2 —CH 2 , CH 2 —N, CH 2 —NR 2 or SO 2 , where
• R 2 is a hydrogen atom; is a C 1 -C 4 alkyl group, such as methyl or ethyl; or is a phenyl group which may be unsubstituted or substituted one or more times by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, trifluoromethyl, nitro, cyano,
• R 1 and n are as defined above and R 20 is hydrogen, methyl or ethyl
• R 3 is a CH 3 , COOCH 3 or COOC 2 H 5 group
• R 4 is a CH 3 or SO 3 H group or a chlorine atom
• p is a number from 0 to 3
• auxiliaries that are employed in the conventional processes, such as surfactants, nonpigmentary and pigmentary dispersants, fillers, standardizers, resins, waxes, defoamers, antidust agents, extenders, shading colorants, preservatives, drying retardants, rheology control additives, wetting agents, antioxidants, UV absorbers, light stabilizers, or a combination thereof.
• the auxiliaries may be added at any point in time before, during or after the reaction in the microjet reactor, all at once or in several portions.
• the auxiliaries may, for example, be added prior to injection to the reactant solutions or suspensions, or else during the reaction in liquid, dissolved or suspended form, by means of a separate jet, by injection into the collision point.
• the overall amount of the added auxiliaries may amount to from 0 to 40% by weight, preferably from 1 to 30% by weight, in particular from 2.5 to 25% by weight, based on the azo colorant.
• Suitable surfactants include anionic or anion-active, cationic or cation-active, and nonionic substances or mixtures of these agents. Preference is given to those surfactants or surfactant mixtures which do not foam in the course of the collision.
• anion-active substances include fatty acid taurides, fatty acid N-methyltaurides, fatty acid isethionates, alkylphenylsulfonates, alkylnaphthalene-sulfonates, alkylphenol polyglycol ether sulfates, fatty alcohol polyglycol ether sulfates, fatty acid amide polyglycol ether sulfates, alkyl sulfosuccinamates, alkenylsuccinic monoesters, fatty alcohol polyglycol ether sulfosuccinates, alkanesulfonates, fatty acid glutamates, alkyl sulfosuccinates, fatty acid sarcosides; fatty acids, such as palmitic, stearic, and oleic acid; soaps, such as alkali metal salts of fatty acids, naphthenic acids and resin acids, such as abietic acid; alkali-soluble salts
• resin soaps i.e., alkali metal salts of resin acids.
• Suitable cation-active substances include quaternary ammonium salts, fatty amine alkoxylates, alkoxylated polyamines, fatty amine polyglycol ethers, fatty amines, diamines and polyamines derived from fatty amines or fatty alcohols, and their alkoxylates, imidazolines derived from fatty acids, and salts of these cation-active substances, such as acetates, for example.
• nonionic substances include amine oxides, fatty alcohol polyglycol ethers, fatty acid polyglycol esters, betaines, such as fatty acid amide N-propyl betaines, phosphoric esters of aliphatic and aromatic alcohols, fatty alcohols or fatty alcohol polyglycol ethers, fatty acid amide ethoxylates, fatty alcohol-alkylene oxide adducts, and alkylphenol polyglycol ethers.
• betaines such as fatty acid amide N-propyl betaines, phosphoric esters of aliphatic and aromatic alcohols, fatty alcohols or fatty alcohol polyglycol ethers, fatty acid amide ethoxylates, fatty alcohol-alkylene oxide adducts, and alkylphenol polyglycol ethers.
• nonpigmentary dispersants substances which structurally are not derived by chemical modification from organic pigments. They are added as dispersants either during the actual preparation of pigments, or else often during the incorporation of the pigments into the application media to be colored; for example in the preparation of paints or printing inks, by dispersion of the pigments into the corresponding binders. They may be polymeric substances, examples being polyolefins, polyesters, polyethers, polyamides, polyimines, polyacrylates, polyisocyanates, block copolymers thereof, copolymers of the corresponding monomers; or polymers of one class modified with a few monomers from another class.
• polymeric substances carry polar anchor groups such as hydroxyl, amino, imino, and ammonium groups, for example, carboxylic acid groups and carboxylate groups, sulfonic acid groups and sulfonate groups, or phosphonic acid groups and phosphonate groups, and may also be modified with aromatic, nonpigmentary substances.
• Nonpigmentary dispersants may also, furthermore, be aromatic substances chemically modified with functional groups and not derived from organic pigments.
• Nonpigmentary dispersants of this kind are known to the skilled worker, and some are available commercially (e.g., Solsperse®, Avecia; Disperbyk®, Byk, Efka®, Efka).
• These basic structures are in many cases modified further, by means for example of chemical reaction with further substances carrying functional groups or by salt formation.
• pigmentary dispersants are meant pigment dispersants which are derived from an organic pigment as the parent structure and are prepared by chemically modifying this parent structure; examples include saccharin-containing pigment dispersants, piperidyl-containing pigment dispersants, naphthalene- or perylene-derived pigment dispersants, pigment dispersants containing functional groups linked to the pigment parent structure via a methylene group, pigment parent structures chemically modified with polymers, pigment dispersants containing sulfo acid groups, pigment dispersants containing sulfonamide groups, pigment dispersants containing ether groups, or pigment dispersants containing carboxylic acid, carboxylic ester or carboxamide groups.
• buffer solutions preferably of organic acids and their salts, such as formic acid/formate buffer, acetic acid/acetate buffer, and citric acid/citrate buffer, for example; or of inorganic acids and their salts, such as phosphoric acid/phosphate buffer or carbonic acid/carbonate or hydrogen carbonate buffer, for example.
• auxiliaries or buffer solutions it is also possible to use different jet reaches or a different number of jets and so to realize, for example, different volume proportions that are required.
• process of the invention it is also possible, through the use of more than one diazonium salt and/or more than one coupling component, to prepare mixtures or else, in the case of solid products, mixed crystals of azo colorants. In this case the reactants may be injected as a mixture or separately.
• the azo colorant is preferably isolated directly following reaction. However, it is also possible to carry out an aftertreatment (finish) with water and/or an organic solvent, at temperatures for example from 20 to 250° C., with or without the addition of auxiliaries.
• the process of the invention is universally suitable for preparing azo colorants obtained in the form of a suspension or in the form of solution.
• the very rapid, intensive mixing of the reactants ensures rapid and complete conversion and hence constant and reproducible reaction conditions and the desired consistency of quality. Instances of clogging, such as occur in the case of the existing microreactors where solid substances are used or produced, can be reliably avoided. Scaleup is also easy, since the drastic changes in surface/volume ratios or mixing ratios that commonly occur, for example, are absent.
• Inventively prepared azo colorants are suitable for coloring natural or synthetic organic materials of high molecular mass, such as cellulose ethers and cellulose esters, such as ethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate, for example, natural resins or synthetic resins, such as addition-polymerization resins or condensation resins, examples being amino resins, especially urea- and melamine-formaldehyde resins, alkyd resins, acrylic resins, phenolic resins, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, and polyacrylates, polyamides, polyurethanes or polyesters, rubber, latices, casein, silicones, and silicone resins, individually or in mixtures.
• natural resins or synthetic resins such as addition-polymerization resins or condensation resins, examples being amino resins, especially urea- and melamine-formal
• the high molecular mass organic compounds mentioned are in the form of plastically deformable masses, casting resins, pastes, melts or spinning solutions, paints, stains, foams, drawing inks, writing inks, mordants, coating materials, emulsion paints or printing inks.
• the azo colorants prepared in accordance with the invention are employed in an amount of preferably from 0.05 to 30% by weight, more preferably from 0.1 to 15% by weight.
• the azo pigments prepared by the process of the invention may be used for example to pigment the industrially commonplace baking varnishes from the class of alkyd-melamine resin varnishes, acrylic-melamine resin varnishes, polyester varnishes, high-solids acrylic resin varnishes, aqueous, polyurethane-based varnishes, and also two-component varnishes based on polyisocyanate-crosslinkable acrylic resins, and especially automotive metallic varnishes.
• the azo colorants prepared in accordance with the invention are also suitable for use as colorants in electrophotographic toners and developers, such as one- or two-component powder toners (also called one- or two-component developers), magnetic toners, liquid toners, addition-polymerization toners, and also specialty toners.
• electrophotographic toners and developers such as one- or two-component powder toners (also called one- or two-component developers), magnetic toners, liquid toners, addition-polymerization toners, and also specialty toners.
• Typical toner binders are addition-polymerization, polyaddition, and polycondensation resins, such as styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester, and phenol-epoxy resins, polysulfones, polyurethanes, individually or in combination, and also polyethylene and polypropylene, which may contain further ingredients, such as charge control agents, waxes or flow aids, or may be subsequently modified with these additives.
• addition-polymerization, polyaddition, and polycondensation resins such as styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester, and phenol-epoxy resins, polysulfones, polyurethanes, individually or in combination, and also polyethylene and polypropylene, which may contain further ingredients, such as charge control agents, waxes or flow aids, or may
• the azo colorants prepared in accordance with the invention are suitable for use as colorants in powders and powder coating materials, especially in triboelectrically or electrokinetically sprayable powder coating materials that are used to coat the surfaces of articles made, for example, of metal, wood, plastic, glass, ceramic, concrete, textile material, paper or rubber.
• Typical powder coating resins employed are epoxy resins, carboxyl- and hydroxyl-containing polyester resins, polyurethane resins and acrylic resins, together with customary curing agents. Combinations of resins are also used. For example, epoxy resins are frequently used in combination with carboxyl- and hydroxyl-containing polyester resins.
• Typical curing components are, for example, acid anhydrides, imidazoles, and also dicyandiamide and its derivatives, blocked isocyanates, bisacylurethanes, phenolic and melamine resins, triglycidyl isocyanurates, oxazolines, and dicarboxylic acids.
• the azo colorants prepared in accordance with the invention a re suitable for use as colorants in inkjet inks on an aqueous and nonaqueous basis, and also in those inks which operate in accordance with the hotmelt process .
• azo colorants prepared in accordance with the invention are also suitable as colorants for color filters, both for subtractive and for additive color generation.
• the azo colorants prepared in accordance with the invention are suitable for dyeing or printing hydroxyl-containing or nitrogenous natural organic and also synthetic substrates.
• substrates include for example synthetic or natural fiber materials and also leather materials comprising predominantly natural or regenerated cellulose or natural or synthetic polyamides.
• they are suitable for dyeing and printing textile material based on acetate, polyester, polyamide, polyacrylonitrile, PVC, and polyurethane fibers and also wool or in particular cotton.
• the dyes may be applied to the textile materials by the usual exhaust, padding or printing processes.
• the solvent fastness was determined in accordance with DIN 55976.
• the fastness to overcoating was determined in accordance with DIN 53221.
• An approximately 5% strength aqueous 3,3′-dichlorobenzidene tetraazo solution with a temperature of 0° C. prepared by bisdiazotizing 253 parts of 3,3′-dichlorobenzidene in dilute HCl and sodium nitrite, is pumped at 26 bar through one of two frontally opposed nozzles, each with a diameter of 300 ⁇ m, of a two-jet microjet reactor.
• Pumped through the second nozzle under the same pressure is an approximately 5% strength aqueous coupling component solution having a temperature of 10° C., prepared by dissolving 354 parts of acetoacetanilide in dilute sodium hydroxide solution, buffered by the addition of 164 parts of sodium acetate.
• the jets impinge on one another frontally in a gas atmosphere.
• the resulting pigment suspension is carried off by a stream of compressed air of about 700 I/h, which serves simultaneously to maintain the gas atmosphere at the collision point of the jet.
• the compressed air stream enters perpendicularly with respect to the two jets, through an opening in the reactor housing.
• the exit opening for the compressed air and the pigment suspension is situated on the opposite side to the entry opening of the compressed air stream.
• the pigment is used to prepare an offset printing ink with a commercially customary heatset offset varnish based on a hard resin in mineral oil.
• the printing ink is notable for markedly higher color strength, significantly higher transparency, and higher gloss.
• the azo coupling takes place in the microjet reactor used in Example 1.
• the diazonium salt solution, at 27 bar, and the solution of the coupling component, at 31 bar, are sprayed against one another through the two nozzles, with the compressed air stream for carrying off the resulting pigment suspension being approximately 700 I/h.
• the resulting pigment suspension is stirred at 40° C. for about 1 h and then filtered and the solid product is washed salt-free with water. The presscake is dried at 80° C. This gives Pigment Red 2.
• the pigment is used to prepare an offset printing ink with a commercially customary heatset offset varnish based on a hard resin in mineral oil.
• the printing ink is notable for high color strength, transparency, and brightness.
• the azo coupling takes place in the microjet reactor used in Example 1.
• the diazonium salt solution and the solution of the coupling component are sprayed at 43 to 45 bar through the two nozzles against one another; the compressed air stream for carrying off the resulting pigment suspension is approximately 700 I/h.
• the temperature of the pigment suspension carried off is from 35 to 40° C.
• the resulting pigment suspension is stirred at about 40° C. for about 15 minutes and then filtered and the solid product is washed salt-free with water.
• the presscake is dried at 80° C. This gives Pigment Red 146.
• the pigment is used to prepare a gravure printing ink with a commercially customary nitrocellulose gravure printing varnish based on a collodium wool in ethyl acetate.
• a printing ink prepared with a commercially customary Pigment Red 146 the printing ink features substantially higher transparency and markedly higher gloss.
• the azo coupling takes place in the microjet reactor used in Example 1.
• the diazonium salt suspension, at about 45 bar, and the solution of the coupling component, at about 34 bar, are sprayed against one another through the two nozzles, the compressed air stream for carrying off the resulting pigment suspension being approximately 1000 I/h.
• 1500 parts of the pigment suspension are heated to 80° C., adjusted to a pH of 2 using aqueous 25% strength hydrochloric acid, and stirred for 15 minutes.
• a solution at a temperature of 80° C. made up of 0.82 part of stearic acid in 10 parts of water and 3 drops of aqueous 33% strength sodium hydroxide solution, and then 30.92 parts of calcium chloride, are added.
• the mixture is filtered with suction and the solid product is washed first with aqueous hydrochloric acid with a pH of 2 and then with water.
• the presscake is dried at 80° C.
• the diazoinium salt suspension is prepared in accordance with Example 4a).
• the solution of the coupling component is prepared in accordance with Example 4b) except that no disodium hydrogen phosphate is added.
• the presscake is dried at 80° C.
• a transparent PVC film is produced with each of the pigments prepared in accordance with Example 4c and Example 4d.
• the pigment prepared inventively in accordance with Example 4c gives a strongly colored, transparent, bright, and pure PVC coloration.
• the pigment prepared conventionally in accordance with Example 4d cannot be dispersed satisfactorily, and the PVC film exhibits distinct specks and is weaker in color.
• the pigment is used to prepare an offset printing ink with a commercially customary heatset offset varnish based on a hard resin in mineral oil.
• the printing ink is notable for markedly higher color strength, significantly higher transparency, and higher gloss.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (3)

Publications (2)

Family

ID=7658693

Family Applications (1)

Country Status (5)

Cited By (27)

Families Citing this family (26)

Citations (9)

• 2000
  • 2000-10-05 DE DE10049200A patent/DE10049200A1/de not_active Withdrawn
• 2001
  • 2001-09-14 EP EP01122054A patent/EP1195411A1/de not_active Withdrawn
  • 2001-09-20 JP JP2001287016A patent/JP2002129050A/ja not_active Withdrawn
  • 2001-10-05 US US09/972,102 patent/US6548647B2/en not_active Expired - Fee Related
  • 2001-10-05 KR KR1020010061466A patent/KR20020027272A/ko not_active Application Discontinuation

Patent Citations (11)

Non-Patent Citations (8)

Also Published As

Similar Documents

Legal Events